Textile finishing treatment with triazine derivatives



United States Patent Int. Cl. D 06m 13/12 US. Cl. 8-1163 13 Claims ABSTRACT OF THE DISCLOSURE Textiles, especially cellulosic textiles, are rendered crease-proof by treatment in a bath containing a compound of the formula:

CH2OH CHz-N C=O CH2N CHzOH wherein R is alkyl from 1 to 8 carbon atoms and an acid catalyst. The thus treated textile is then thermofixed at 140 to 180 C. for one to five minutes.

The present invention relates to 1,3-bis-hydroxymethyl-- 2-one-S-alkylcarboxylate-1,3,5-hexahydrotriazines, wherein the alkyl group contains 1 to 8 carbon atoms, and to the use thereof in finishing baths for cellulosic textile materials. It also relates to the finishing baths and to the textile materials finished with the said compounds contained in the said baths.

Natural or artificial textile materials, such as cotton and rayon, have a tendency toward becoming irreversibly creased or crumpled, because of the low spn'nginess of the constituent fibers thereof. This is why the washing of such textile materials has to be followed by an ironing operation to smooth out creases and folds formed during the laundering operation.

Commercial treatments, known for instance as anticrurnple, wash-and-wear, no-iron, etc., intended to palliate undesired crumpling of the textile materials, in the dry state or in the wet state with carry-over to the material when dried, involve the use of very diverse products. Sullice it to enumerate, among such products, certain methylol derivatives of nitrogenous organic compounds, such as cyanuric acid, carbamic esters, urea, melamine, ethyleneurea, etc. The action of these derivatives, especially when they contain two reactive methylol groups and when used together with catalysts, seems to involve cross-linking of the cellulose molecules with formation of ether bridges.

Some resins, notably the alkyl dimethylol-car-bamate resins, prove to be relatively difiicult to condense and develop maximum effect only at the cost of dynamometric strength losses which are prohibitive in most cases. Moreover, the permanence of the finish is rather limited timewise.

Textile materials treated with most of the aforesaid agents suffer substantial deterioration after being bleached with hypochlorite-based or hypochlorite-generating products. In addition, in some cases, the treated fabric is rough to the touch and require additional treatments with auxiliary softening agents.

Other resins, of the triazone class, formed by reacting amines or alkanolamines with dimethylol urea, are excellent finishes for cellulosic materials and make it possible to overcome most of the aforesaid drawbacks. However,

3,521,996 Patented July 28, 1970 &

the disagreeable and long-lasting odor due to the amine salts necessitates washing of the treated fabrics. Moreover, it is frequently necessary to resort to auxiliary washing agents to improve the feel.

The present invention is concerned with finishing materials which make possible the total elimination of the aforesaid drawbacks. When applied to cellulosic textile materials, they will impart thereto outstanding selfsmoothing properties in the wet, moist or dry state, as well as definitive stabilization of dimensions and particularly soft feel, these characteristics being specific to the treatment with the said finishing agents of this invention. The so-treated materials can be bleached with any of the conventionally employed bleaching agents, including those which are hypochlorite-based. They can be laundered without affecting the finish or the outlined desirable properties imparted thereto. Finally, due to the absence of any disagreeable odor, it is possible in most cases to forego washing aftertreatment.

The active compounds according to the present invention are of the following formula:

CHQOH (3112011 (I) wherein R is alkyl with from 1 to 8 carbon atoms, e.g. methyl, ethyl, propyl, isopropyl, butyl, isobutyl, pentyl, hexyl, octyl, etc.

The 1,3-bis-hydroxymethyl-Z-one-S-alkylcarboxylate-1, 3,5-hexahydrotriazines I of the preceding formula can be prepared according to the following methods, quantitative yields being obtained throughout:

(1) Dimethylol urea, obtained from urea and formaldehyde, is condensed with one or more C to C -alkyl carbamates in equimolecular proportions relative to the starting urea, the condensation being followed by dimethylolation with formaldehyde in alkaline medium.

(2) Formaldehyde is reacted with one or more C to C -alkyl carbamates, and the resultant N-dimethylol alkyl carbamate is condensed with urea, after which the obtained triazone is dimethylolated with formaldehyde in alkaline medium.

(3) Formaldehyde is reacted with an equimolecular mixture of one or more C,- to C -alkyl carbamic acid esters and urea in aqueous solution, after which, as in the other methods, dimethylolation of the resultant triazine is carried out with formaldehyde in alkaline medium.

(4) The reaction between urea, one or more C to C alkyl carbamic acid esters, and excess formaldehyde is carried out in a single stage.

The hydrotriazinone derivatives of the invention have two reactive positions in the molecule, like dimethylolethyleneurea, but the absence of replaceable hydrogen atoms prevents fixation of chlorine during the bleaching of the treated cellulosic materials with hypochlorite. Moreover, the soft feel of fabrics finished with 1,3- bishydroxymethyl-2-one-S-alkylcarboxylate 1,3,5 hexahydrotria-zine (I) of this invention is ascri'bable to plasticizetion due to the ester group.

Whatever method of preparation is employed, there is obtained a more or less dilute solution of one of the hydrotriazone derivatives (I), and this solution is brought to the desired concentration, between 5% and 20% by weight, in accordance with the nature of the textile material to be treated. This solution has added thereto an acidic catalyst such as an organic acid, an inorganic salt of strong acid, an amine salt, etc. alone or in admixture and, in appropriate cases, auxiliary agents such as wetting agents, lubricants, brightening agents, etc.

The catalytically active inorganic salts of strong acids, such as magnesium chloride hexahydrate, zinc chloride, zinc nitrate hexahydrate, magnesium nitrate, etc., are used in the proportion of 0.5% to 4% relative to the total weight of the treating bathi.e. in a 0.5% to 4% con-' centrationwhile organic acid catalysts, such as formic acid, acetic acid, maleic acid, tartaric acid, lactic acid or citric acid, are used in a lower concentration of 0.1% to 0.6% by weight.

The finishing operation is carried out in per se conventional manner by foularding and then expressing to an uptake of the order of 50 to 100% by weight, drying at 60 to 110 C., and final thermofixing at 140 to 180 C. for 1 to 5 minutes, depending upon the temperature employed.

Although afterwashing of the finished material is not necessary, it is recommendable in certain cases to eliminate products, such as unreacted catalyst. This is especially recommendable in the case of white textile fabrics, particularly when use has been made of zinc nitrate as catalyst, which may decrease the stability to light of optical brightening agents.

The following examples set forth presently preferred embodiments of the invention, solely by way of illustration, and are not intended to be limitative in any respect.

EXAMPLE 1 An aqueous solution of formaldehyde, containing 400 grams of formaldehyde per liter, is stabilized with methanol in per se conventional manner. The pH of the resultant formol solution (methanol-stabilized aqueous formaldehyde solution) is then adjusted to 9.5 by the gradual addition thereto of concentrated aqueous caustic soda solution.

The obtained solution is then heated to about C., whereupon 600 grams of urea and then 750 grams of methyl carbamate are added. During the dissolution, the temperature of the mixture drops about 20 degrees; however, after the ensuing exothermic reaction has started, the temperature is soon brought up to its initial value. The reaction lasts about one hour. The solution is acidified up to pH 4, and is then heated to C. for one hour.

Dihydroxymethylation (dimethylolation) is effected by adding 1.5 liters of formol solution (containing 400 grams of formaldehyde per liter and being stabilized with methanol), and then adding aqueous caustic soda solution to bring the pH up to 9.5.

The reaction mixture is allowed to stand for about 12 hours, whereupon acidification is carried out until the pH is brought to neutrality.

The final solution, which contains 425 grams of 1,3-bishydroxymethyl 5 methylcarboxylate-Z-one-1,3,5-hexahydrotriazine per liter is quite clear. The stability thereof is excellent even after several months storage. The characteristics of the product are as follows, F, C and MC standing for formol, urea and methyl carbamate respectively:

Total F (U-i-MC) 2.5 Combined F (U+MC) 1.95 Free P (U-i-MC) 0.55 dd, 1.148 pH 7 A piece of mercerized and bleached poplin (weighing 140 grams per square meter), conditioned for 24 hours in a controlled atmosphere (20 0, 6 5% relative humidity) is impregnated by immersion in the said bath and is then expressed (squeezed) to a wet take-up of approximately 66% by Weight. The piece of cloth is then mounted on a pin frame having the exact dimensions of the fabric prior to impregnation of the latter, the essential object of this operation being to avoid any shrinkage before thermofixation is effected and which, by altering the number of threads per unit area, might 'be the source of errors (higher readings) in resistance measurements.

Drying and thermofixation are then carried out for 10 minutes at C. and for 4 minutes at 160 C., respectively.

After a simple rinsing with Water, followed by drying at 90 C. and conditioning (for 24 hours at 20 C. and 65% relative humidity), the finished piece of cloth has a warp and weft crease-recovery angle of 155 and 154 respectively (crease-recovery angles being determined according to ASTM D. 1424, 56 T). Measurements carried out on the treated piece of cloth, before drying, and untreated control, gave angle values of 146 and 94/ 86 respectively.

The warp and weft average dynamometric resistance measured on 5 cm. wide test-pieces with a distance of 25 cm. between clips is 36.75 kg. and 28.6 kg., as against 57 kg. and 43 kg. for untreated cloth.

Neither yellowing nor appreciable decrease in dynamometric resistance of thus-finished fabrics are noted after chlorination and passage between two heating plates, after the manner of the tests described in the AATCCs standard draft (Tentative Test Method 69-4958, Damage Caused by Retained Chlorine, and Scorch Tests).

Poplin specimens finished according to the present example were subjected to successive washings for 12 minutes each at 85 C. in a washing machine, in washwater containing 5 grams per liter of soap flakes. After 15 washes, the crease-recovery angles and warp and weft dynamometric resistance were maintained at 142/14,5 and 33 kg./25.6 kg. respectively. The washed specimens showed essentially no shrinkage (0.5 maximum). Moreover, the scorch test procedure produced minimal drop in warp resistance (only 4%).

EXAMPLE 2 The pH of a formol solution, stabilized with methanol and containing 400 grams of formaldehyde per liter, is adjusted to 8.5. 600 grams of urea are added to 1.5 liters of such solution at ambient temperature (15 to 30 C.). After two hours reaction, 890 grams of ethyl carbamate are added to the reaction mixture, which is then acidified to pH. Reaction ensues for one hour at 50 C., after which 2.25 liters of the formol solution are added and the pH adjusted to 9. After several hours, the pH was down to 7 and the solution contained 425 grams per liter of 1,3 bis-hydroxymethyl-2-one 5 ethylcarboxylate-1,3,5-hexahydrotriazine.

A piece of fabric similar to that employed according to Example 1 is treated under the same conditions as in the said example, in an aqueous finishing bath containing 165 grams per liter of the last-mentioned solution and 2 grams per liter of tartaric acid as catalyst.

The warp and weft crease-recovery angles of the thustreated fabric are 146 and 150 respectively, and the dynamometric resistance is 35 kg. and 29 kg. respectively.

EXAMPLE 3 750 grams of methyl carbamate are added to 2.25 liters of 400 g./liter-formol solution stabilized with methanol. The resultant solution (pH 9) is heated to 50 C. After one hours reaction at this temperature, 600 grams of urea are added to the reaction mixture, the pH adjusted to 4, and the reaction allowed to proceed for about one hour before adjusting the pH to 9.5. After about 12 hours standing at ambient temperature and neutralization, the solution contains 425 grams per liter of 1,3-bis-hydroxymethyl-2-one-S-methylcarboxylate 1,3,5 hexahydrotriazine. Poplin as described in Example 1 is subjected to the same treatment in an aqueous finishing bath containing Grams/ liter 425 g./liter-hydrotriazone solution 130 Zinc nitrate hexahydrate The pH of the finishing bath is adjusted to 4.8 before immersion impregnation therein of the piece of poplin, which is then squeezed down to 68% wet before being dried at 90 C. and subjected to thermofixation at 180 C. for 70 seconds.

Measurements of warp and weft crease-recovery angles and dynamometric resistance gave the following figures respectively: 149/152 and 37.2 kg./27.4 kg.

Cotton, wool, rayon, silk and other textile fabrics can be similarly finished.

What is claimed is:

1. A textile finishing bath consisting essentially of an aqueous solution of a compound of the formula:

OHzOH (I) in a concentration of from about 5% to about said solution also containing from about 0.1% to about 4.0% by weight of an acid catalyst.

2. A finishing bath according to claim 1, wherein R in compound I is methyl.

3. A finishing bath according to claim 1, wherein R in compound I is ethyl.

4. A finishing bath according to claim 1, wherein the catalyst is an organic acid catalyst in an amount from 0.1% to 0.5% by weight.

5. A finishing bath according to claim 1, wherein the catalyst is an inorganic metal salt of a strong acid in an amount from 0.5 to 4.0% by Weight.

6. A finishing bath according to claim 4, wherein the catalyst is selected from the group consisting of tartaric acid, lactic acid and citric acid.

7. A finishing bath according to claim 5, wherein the catalyst is selected from the group consisting of magnesium chloride, zinc nitrate and zinc chloride.

8. In the crease-proofing of textile material by impregnation thereof with a crease-proofing agent followed by thermofixation at 140 to 180 C. for 1 to 5 minutes of the said agent on the fiber, the improvement according to which the material is impregnated with a compound of the formula:

CHzOH CHz-N R-O-C O-N C=O CHz-N OH2OH wherein R is alkyl with from 1 to 8 carbon atoms said thermofixation being carried out at to C. for 1 to 5 minutes.

12. Cellulosic textile material according to claim 11, R in the compound of Formula I being methyl.

13. Cellulosic textile material according to claim 11, R in the compound of Formula I being ethyl.

References Cited UNITED STATES PATENTS 3,301,631 1/1967 Mauldin 8ll6.2 3,152,111 10/1964 Taber 260-153 3,035,942 5/1962 Cooke.

FOREIGN PATENTS 966,283 8/1964 Great Britain.

GEORGE F. LESMES, Primary Examiner B. BE'ITIS, Assistant Examiner US. Cl. X.R. 

